Lubricant compositions comprising substituted indans

ABSTRACT

IN WHICH R is at least one member of the group consisting of hydrogen, alkyl, phenyl, carboxy alkyl, carboxy phenyl, phenoxy and their thiosubstituted derivatives. The method for the preparation of these substituted indans is also provided. Lubricant compositions are provided comprising a substituted indan having the structure:   D R A W I N G

United States Patent Gemmill, Jr. et a1.

Feb. 8, 1972 [54] LUBRICANT COMPOSITIONS COMPRISING SUBSTITUTED INDANS[72] Inventors: Robert M. Gemmill, Jr., W0odbu 'y; John W. Schick,Cherry Hill, both of NJ.

[73] Assignee: Mobil Oil Corporation [22] Filed: June 24, 1969 [21]Appl. No.2 836,161

[51] lnt. Cl ..Cl0m 1/16,C10m 1/38, ClOm 1/20 [58] Field of Search..252/52, 59, 45, 73

[56] References Cited UNITED STATES PATENTS 2,953,609 9/ 1960 Wadsworthet a1. ..252/45 X 2,968,678 l/1961 Oswald ....252/45 X 3,006,852 10/1961Barnum et a1. ..252/52 3,036,138 5/1962 Mingasson et a1. ....252/52 X3,098,103 7/1963 Reifschneider et a1. ....252/45 X 3,161,692 12/1964McLaughlin et al. ..252/59 X Y mensw- 57 ABSTRACT Lubricant compositionsare provided comprising a substituted indan having the structure:

in which R is at least one merit Ber biiiigrfififi consisting ofhydrogen, algyb phenyl, carboxy alltyl c arhoigx phenyl,

ph enoxy and their thiosubstituted derivatii/es. The method for thepreparation of these substituted indans is also 5 Claims, No DrawingsLUBRICANT COMPOSITIONS COMPRISING SUBSTITUTED INDANS BACKGROUND OF THEINVENTION 1. Field of the Invention 5 This invention relates tolubricant compositions, and, in one of its aspects, relates moreparticularly to lubricant compositions which are thermally andoxidatively stable and exhibit reduced tendency to deterioration. Stillmore particularly, in this aspect, the invention relates to suchlubricant compositions as lubricant oils and greases, and also to otherforms of organic media, in which these lubricants can be employed asblending stocks to modify their properties, for example such organicmedia as automatic transmission fluids, hydraulic fluids, heat-exchangefluids, and the like, in which the aforementioned stability againstthermal and oxidative deterioration is an important requisite.

2. Description of the Prior Art The importance of maintaining thermaland oxidative stability in lubricant compositions, for example, in suchrepresentative areas as hydrocarbon lubricant oils and greases, or inany of the other aforementioned areas, is well known. Prior to thepresent invention, various lubricants or lubricant additives have beensuggested for such purpose but have not been found to provide thedesired degree of improvement. In some aspects either, or both,oxidative stability and thermal stability have not been significantlyimproved in the aforementioned compositions. In other instances,lubricants or lubricant additives employed for such purpose have provedto be costly, far 30 outweighing the degree of improvement obtained.

Summary of the Invention in which R is at least one member of the groupconsisting of hydrogen, alkyl, phenyl, carboxy alkyl, carboxy phenyl,phenoxy, and their thiosubstituted derivatives.

These substituted indans, as more fully hereinafter described, have beenfound to be markedly effective not only in possessing thermal andoxidative stability as lubricants, per se, but also in imparting, as ablending stock, thermal and oxidative stability to lubricantcompositions in the form of lubricant oils, greases and any of theaforementioned organic media such as automatic transmission fluids,hydraulic fluids, heat-exchange fluids and the like.

The organic compositions, of more specific importance, which areimproved by blending with the substituted indans of the presentinvention may include mineral oils and synthetic oils of lubricatingviscosities. Of particular significance is the improvement of petroleumdistillate lubricating oils having boiling points as high as 650 F. orabove and also mixtures of such oils. It should be noted, in thisrespect, that the term distillate oils is not intended to be restrictedto straight-run distillate fractions. These distillate oils can bestraight-run distillate oils, catalytically or thermally cracked(including hydrocracked) distillate oils, or mixtures of straight-rundistillate oils, naphthas and the like, with cracked distillate stocksand may be of varying viscosities and pour points. Moreover,

such oils can be treated in accordance with well-known commercialmethods, such as acid or caustic treatment, hydrogenation, solventrefining, clay treatment, and the like.

As previously indicated, the aforementioned substituted indans may alsobe incorporated, as blending agents in lubricant vehicles of greasecompositions. Such greases, may comprise a combination of a wide varietyof lubricating vehicles and thickening or gelling agents. Thus, greasesin which the aforementioned substituted indans are particularlyeffective as vehicle blending agents may comprise any of theconventional hydrocarbon oils of lubricating viscosity, as the oilvehicle, and may include mineral oils or mineral oils in combinationwith synthetic lubricating oils, aliphatic phosphates, esters anddidesters, silicates, siloxanes and oxalkyl ethers and esters. Minerallubricating oils, preferably employed as the lubricating vehicle, may beof any suitable lubricating viscosity range from about 45 SSU at l00 F.to about 6,000 SSU at 100 F., and, preferably, from about 500 to about250 SSU at 210 F. These oils may have viscosity indexes varying frombelow 0 to about 100 or higher. Viscosity indexes from about 70 to aboutare preferred. The average molecular weights of these oils may rangefrom about 250 to about 800. The lubricating oil is employed in thegrease composition in an amount sufficient to constitute the balance ofthe total grease composition, after accounting for the desired quantityof the thickening agent, and other additive components to be included inthe grease formulation.

As previously indicated, the oil vehicles employed in the novel greaseformulations of the present invention, in which the aforementionedsubstituted indans are incorporated as blending agents, may comprisemineral oils or combinations of mineral oils with synthetic oils oflubricating viscosity. When high temperature stability is not arequirement of the finished grease, mineral oils having a viscosity ofat least 40 SSU at F., and particularly those falling within the rangefrom about 60 SSU to about 6,000 SSU at 100 F. may be employed. Ininstances, where synthetic vehicles are employed in addition to mineraloils, as the lubricating vehicle, various compounds of this type may besuccessfully utilized. Typical synthetic vehicles include:polypropylene, polypropylene glycol, trimethylol propane esters,neopentyl and pentaerythritol esters, di-(2-ethyl) hexyl) sebacate,di-(2-ethyl hexyl) adipate, dibutyl phthalate, fluorocarbons, silicateesters, silanes, esters of phosphorus-containing acids, liquid ureas,ferrocene derivatives, hydrogenated mineral oils, chaintype polyphenyls,siloxanes and silicones (poly-siloxanes), alkyl-substituted diphenylethers typified by a butyl-substituted bis (p-phenoxy phenyl) ether,phenoxy phenyl ethers, etc.

The lubricating vehicles of the aforementioned improved greases of thepresent invention containing the abovedescribed substituted indans asblending agents, are combined with a grease-forming quantity of athickening agent. For this purpose, a wide variety of materials may beemployed. These thickening or gelling agents may include any of theconventional metal salts or soaps, which are dispersed in thelubricating vehicle in grease-forming quantities, in such degree as toimpart to the resulting grease composition, the desired consistency.Other thickening agents that may be employed in the grease formation maycomprise the nonsoap thickeners, such as surface-modified clays andsilicas, aryl ureas, calcium complexes and similar materials. Ingeneral, grease thickeners may be employed which do not melt anddissolve when used at the required temperature within a particularenvironment; however, in all other respects, any materials which arenormally employed for thickening or gelling hydrocarbon fluids forforming greases, can be used in preparing the aforementioned improvedgreases in accordance with the present invention.

The substituted indans of the present invention may be prepared, ingeneral, by subjecting a mixture of an isopropyl aromatic compound and ahalogen to a temperature sufficiently high to effect halogenation of theisopropyl group. Thereafter the halogenated isopropyl aromatic compoundAs previously indicated, the halogenated isopropyl aromatic I compoundis subjected to an elevated temperature at which this compound isconverted to its corresponding substituted indan. In a preferredembodiment the halogenated isopropyl aromatic compound is subjected toan elevated temperature within the range from above the halogenationtemperature employed, but not higher than the boiling point of thehalogenated isopropyl aromatic compound. Preferably the halogenatedisopropyl aromatic compound, for most purposes, is subjected to atemperature from about 100 C. to about 200 C. at which the correspondingsubstituted indan is produced.

As hereinbefore indicated, the halogenated isoproyl aromatic compound issubjected to elevated temperature, in the presence of an acidiccatalyst, for conversion to the corresponding substituted indan. Forthis purpose any acidic material that has an ionization constant greaterthan about lX10 may be employed, and, exemplary thereof, are catalystscomprising a crystalline alumino-silicate zeolite catalyst in anamorphous silica-alumina matrix; sulfuric acid, trichloroacetic acid;monochloroacetic acid on the aforementioned alumino-silicate zeolitecatalyst, phosphoric acid, nitric acid and other organic and inorganicacids having the aforementioned ionization constant.

DESCRIPTION OF SPECIFIC EMBODIMENTS The following examples will serve toillustrate the novel substituted indans of the present invention, themethod for their preparation and their utility in organic lubricatingmedia.

EXAMPLE 1 Dimers of Monoisopropylbiephenyl To a stirred pot containing392 grams (2.0 moles) of monoisopropylbiphenyl and 1,176 grams 15.1moles) of benzene at a temperature between about 0 C. and about C. wasadded dropwise 324 grams (2.03 moles) of bromine. A light source,comprising a lOO-watt clear light bulb, was placed alongside the pot.After 100 hours, I-IBr evolution ceased, indicating completion of thereaction. The benzene was distilled off at reduced pressure leaving aquantitative yield of 551 grams of product. Upon analysis it was foundthat the molecular weight of the product was 275 (225 calculated) andthe bromine'content was 27.6 percent (29.1 percent calculated).

The dimerization reaction was performed, employing 280 grams (1.0 mole)of the above-described brominated product with 2.8 grams 1 percent byweight) of a crushed crystalline alumino-silicate zeolite catalyst in anamorphous silica-alumina matrix at 150 C. in a stirred flask for aperiod of 40 hours. The reaction was considered complete when successivesamples showed no change by gas chromatographic analysis. The product(209.2 grams) was filtered in order to remove the catalyst and wasdissolved in benzene. After washing the benzene solution to neutralitywith water, the benzene was removed and the product was fractionallydistilled under reduced pressure. Gas chromatography showed the productmixture to comprise 25 percent, by weight, of monoisopropylbiphenyl,55-60 percent of the four expected isomeric dimers and 20 percent ofpolymer. Four isomeric dimers were the result of a diisomericmonoisopropylbiphenyl charge stock. The chemical and physical propertiesobtained are hereinafter disclosed in'Table I. The substituted indan,thus produced, can be depicted as having the structure:

EXAMPLE 2 Codimers of Monoisopropylbiphenyl and Alpha-methyl Styrene Twohundred eighty grams (1.0 mole) of the brominated monoisopropylbiphenylfrom Example 10 was reacted with 118 grams (1.0 mole) of alpha-methylstyrene in the presence of 8.0 grams (2 percent by weight) of the acidicclay catalyst of Example 1 at a temperature of about C. in a stirredflask. After 47 hours, 331.8 grams (312 grams calculated) of theresulting product was recovered, in the manner described in Example 1.Gas chromatography showed unreacted monoisopropylbiphenyl (approximately15 percent by weight), alpha-methyl styrene (approximately 24 percent byweight), the four expected codimers (approximately 37 percent byweight), and the four expected dimers of monoisopropylbiphenyl(approximately 24 percent by weight). The product mixture was thenfractionally distilled at reduced pressure. The chemical and physicalproperties obtained are hereinafter disclosed in Table I. Thesubstituted indan thus produced can be depicted as having the structure:

EXAMPLE 3 Dimers of Cumylphenylether (Phenoxy-cumene) Two hundred twelvegrams 1.0 mole) of Cumylphenylether in 590 grams (7.6 moles) of benzenewas brominated with grams (1.0 mole) of bromine in the manner describedin Example The brominated product, following benzene removal, amountedto 308 grams (291 calculated) and had a molecular weight of (296 (291calculated) and a bromine content of 26.2 percent (27.5 percentcalculated). Dimerization of this material was carried out employing 154grams (0.53 mole) of the brominated material and 4.6 grams (3 percent)of the acidic clay catalyst of Example 1 at a temperature of about 150C. for a period of 16 hours. The resulting product was filtered andwashed to neutrality. Gas chromatography showed the resulting productmixture to comprise approximately 49.0 percent cumylphenylether, 7.7percent of a side product, 6.3 percent of the four expected dimers and37.0 per cent of polymer. Analysis of the side product (comprising approximately six components) showed an average molecular weight of 293and a bromine content of 21.1 percent. The chemical and physicalproperties of the substituted indan product are hereinafter disclosed inTable I. The substituted indan thus produced can be depicted as havingthe structure:

EXAMPLE 4 and CH1 i EXAMPLE 5 Codimer of Thiophenoxycumene and Cumene Acodimer of thiophenoxycumene and cumene can be prepared by substitutingthe same molar quantities of thiophenoxycumene in place of cumylphenylether in Example 4 to produce a compound having the followingproperties:

Calculated Found Molecular weight 344 344 Carbon in 83.72 82.11 Hydrogen311 6.98 6.76 Oxygen O 0.56 Sulfur k 9.30 9.80

The chemical and physical properties are hereinafter disclosed in Tablel. The substituted indan thus produced can be depicted as havingthestructure:

TABLE I Example 1 2 3 4 5 Molecular weight 388 812 420 328 344 Bromlnecontent, pereent 0. 42 1.19 0.19 0. 15 0 Chlorine content, percent. 0 0(l 0 0 0 0. 6 0 0 I 0 0 0 0 0 0 515 435 490 425 450 580 510 585 465 515+120 +65 +110 +45 +45 Elolld 3, 806 10, 571 400. 9 468. 9 130 14. 68 28.66 9. 10 9. 86 1. 55 1. 40 AIT, F 830 810 875 870 830 Thefmal steblllty,785 F., 90

Percent loss 0. 007 0. 003 0. 086 0.010 0. 13 v 4, 0% 454. 3 131. 5 14.94 28. 40 8. 40 9. 79 TAN 0. 08 0. 31 0. 49 0. 04 OX./corr., 450 F.:

Akv., percent, F l8. 3 5t Akv., percent, 210 F. 2,900 184 4. 3 6.0 5 TAN2. 1 3. 7 0. 22 D. 44 50 0 5m 5 (b) 5th) 5th) 50) 5(1)) am am 0):. Corn,450 F., no metals:

Akv., percent, 100 F 20. 7 5 Akv., percent, 210 F- 6. 1 5 TAN 0. 51 51Sludge- 0 5 5 Sulfur 9 2%. b crystallized in pure form after severaldays.

From the foregoing data and examples, it will be apparentv that thenovel substituted indans of the present invention possess chemical andphysical characteristics which make them particularly adaptable for useas lubricants, per se, or as blending materials having a wide variety oflubricant compositions for imparting thermal and oxidative stability.Although the present invention has been described herein by means ofcertain specific embodiments and illustrate examples, it is not intendedthat the scope thereof be limited in any way, and is capable of variousmodifications and adaptations, as those skilled in the art will readilyappreciate.

We claim:

1. An organic lubricant composition containing, lubricating amounts ofan organic lubricant mixed with lubrication improving amounts of asubstituted indan having the structure:

in which R is at least one member of the group consisting of hydrogen,phenyl, phenoxy and thiophenyl and wherein not more than one R ishydrogen.

2. A composition as defined in claim 1 wherein said organic lubricantcomprises a hydrocarbon lubricant.

3. A composition as defined in claim 1 wherein said organic lubricant isselected from the group consisting of mineral oils and synthetic esteroils.

4. A composition as defined in claim 1 wherein the synthetic ester oilcomprises a pentaerythritol ester.

5. A composition as defined in claim 1 wherein said organic lubricantcomprises a grease.

"H050 UNITED STATES PATENT OFFICE CERTIFICATE 0F CORRECTEON Patent No.870 Dated Febriuary 97 Inventor) ROBERT M. GEMMILL, JR. and JOHN W.SCHICK I It is certified that error appears in the above-identifiedpatent and that said Letters Patent are hereby corrected as shown below:

Column 2, line 18 "500" should read 5O Column 3, line 27 1 X 10 shouldread 1 X '10' Column 3, line 53 "(225 calculated)" should read (275calculated) Column L line l6 "10" should read l Columh 5, line 13 inExample L diagram 1 "CH should read CH Column 6, line 29 in Table Iunder Example 5 "9 2%" should read 9.2%

Signed and sealed this 3rd day of October 1972.

(SEAL) Attest':

EDWARD MOFLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer a Commissionerof Patents

2. A composition as defined in claim 1 wherein said organic lubricantcomprises a hydrocarbon lubricant.
 3. A composition as defined in claim1 wherein said organic lubricant is selected from the group consistingof mineral oils and synthetic ester oils.
 4. A composition as defined inclaim 1 wherein the synthetic ester oil comprises a pentaerythritolester.
 5. A composition as defined in claim 1 wherein said organiclubricant comprises a grease.